Method for manufacturing radiographic image conversion panel and radiographic image conversion panel produced by the method

ABSTRACT

A method for manufacturing a radiographic image conversion panel having a photostimulable phosphor layer on a support. The method includes: setting a distance between a photostimulable phosphor basic material and a substrate 7 to 60 cm; controlling a temperature of the substrate; and evaporating the photostimulable phosphor basic material in a vacuum of 1.0×10 −2  Pa with an evaporation speed of 0.5 μm/min or more, to form a photostimulable phosphor in the photostimulable phosphor layer by a vapor phase method. The evaporation speed is preferably in a range of 0.5 to 10 μm/min.

BACKGROUND

[0001] 1. Technical Field

[0002] The present invention relates to a method for manufacturing aradiographic image conversion panel and the radiographic image(hereinafter also referred to as a radiograph) conversion panel obtainedby the manufacturing method.

[0003] 2. Description of the Related Art

[0004] In earlier technology, so-called radiography in which silver saltis used to obtain a radiological image has been utilized. However, themethod for imaging a radiological image without silver salt has beendeveloped. That is, the method of imaging by a phosphor absorbing theradial ray transmitted through a subject in a phosphor, thereafter,excited by certain type of energy, and radiating radiological energyaccumulated in the phosphor as fluorescence, is disclosed.

[0005] A concrete example of a radiographic image conversion method isknown, in which a panel comprising and a photostimulable phosphor layerprovided on a support (hereinafter also referred to as base material) isapplied, and both of/either visible light and/or infrared light is usedas excitation energy (see U.S. Pat. No. 3,859,527).

[0006] A radiographic image conversion method using a photostimulablephosphor of higher luminance and sensitivity has been developed. Aradiographic image conversion method using a BaFX: Eu²⁺ system (X: Cl,Br, I) phosphor disclosed in JP Tokukaisho-59-75200A, a radiographicimage conversion method using an alkali halide phosphor disclosed insuch as JP Tokukaisho-61-72087A, and an alkali halide phosphorcontaining metals of Tl⁺ Ce³⁺, Sm³⁺, Eu³⁺, Y³⁺, Ag⁺, Mg²⁺, Pb²⁺ and In³⁺as a co-activator disclosed in JP Tokukaisho-61-73786A and 61-73787A arethe examples.

[0007] In late years, in analysis of a diagnostic image, a radiographicimage conversion panel having higher sharpness has been required.

[0008] As a method for improving the sharpness, for example, attempts ofcontrolling the shape of photostimulable phosphor itself have been madein order to improve sensitivity and sharpness.

[0009] One of these attempts is, for example, a method of using a finequasi-columnar photostimulable phosphor layer deposited on a supporthaving a fine concavoconvex pattern, which is disclosed on JPTokukaisho-61-142497A.

[0010] Further, the following methods and the like are also proposed; asdisclosed in JP Tokukaisho-61-142500A, a method of using a radiographicimage conversion panel having a photostimulable phosphor layer in whichthe cracks of a columnar photostimulable phosphor deposited on a supporthaving a fine pattern are further developed with shock-treatment; asdisclosed in JP Tokukaisho-62-39737A, a method of using a radiographicimage conversion panel having a photostimulable phosphor layer crackedfrom the surface side to be quasi-columnar pattern; and, as disclosed inJP Tokukaisho-62-110200A, a method of forming a photostimulable phosphorlayer having pores onto a support by deposition, subsequently the poresdevelopped to be cracks with heat treatment.

[0011] In addition, in JP Tokukaihei-2-58000A, a radiographic patternconversion panel is described which has a photostimulable phosphor layerwhere strip columnar crystals with a definite slope against a normalline of a support are formed on the support by a vacuum deposition filmformation method.

[0012] In late years, a radiographic image conversion panel using alkalihalide such like CsBr as a base material is proposed. Especially when Euis used as an activator, the improvement of X ray conversion efficiency,which has not achieved before, is expected.

[0013] However, diffusion of Eu due to heat is remarkable and Eu has anature that vapor pressure under vacuum is high. Thus, Eu is easilydispersed in the host and a problem has occurred where Eu exists withuneven distribution in the host. As a result, it has been difficult toobtain high X-ray conversion efficiency by using and activating Eu, andEu did not come into practical use in the market.

[0014] In activators of rare earth elements by which high X-rayconversion efficiency is obtained, the vacuum deposition film formationmethod influences heat distribution of a substrate because heating atthe deposition becomes radiant heat of the substrate.

[0015] This heat distribution is also changed by a degree of vacuum,crystal growth becomes uneven by the heat distribution, and rapiddisturbance occurs in luminance and sharpness. In the vacuum depositionformation method, it has been difficult issues to control theseperformances.

[0016] Therefore, in the vacuum deposition film formation method,particularly when rare earth elements such as Eu are used, only bycontrolling the vapor pressure property, it has been difficult toaccomplish the high X-ray conversion efficiency.

[0017] Also in the vacuum deposition film formation method, utilizationefficiency of primary materials is only several percents to 10%. Thus,the product has become expensive and lacked a multipurpose property (seee.g., JP-Tokukaihei-10-140148A; JP-Tokukaihei-10-265774A).

[0018] Meanwhile, there is barium iodide such as BFX:Eu (X=halogen atom)as a compound conventionally practically used in a coating typephotostimulable phosphor layer. It is inexpensive, but the compound ispoor in transparency at a luminescent region of 390 to 410 nm. There hasbeen problematic in that scattering on particle surfaces becomesremarkable and the sharpness is reduced.

[0019] Meanwhile, particularly when utilized for the use of mammography,the high sharpness is required. Thus, it is necessary to use aradiographic image conversion panel where a phosphor layer is made athin film. When a thin film is formed by the vacuum deposition filmformation method (deposition plate method) and alkali halide crystalsare made into columnar shapes, it has been found that a crystal shapebecomes thin at a substrate side and thick at a surface side, thecrystal in triangular pyramid shape is obtained, and in the crystalparticularly with a film thickness of less than 120 μm, a filling factorof a phosphor in a phosphor layer is low, and the sharpness and an X-rayabsorption amount are extremely poor (see e.g.,JP-Tokukaihei-10-140148A; JP-Tokukaihei-10-265774A).

[0020] Therefore, in the market, a radiographic image conversion panelwhich is excellent in luminance, sharpness and X-ray conversionefficiency (X-ray absorption amount) and a method for manufacturing theradiographic image conversion panel have been required.

SUMMARY

[0021] In accordance with a first aspect of the invention, the methodfor manufacturing a radiographic image conversion panel having aphotostimulable phosphor layer on a support, comprises: setting adistance between a photostimulable phosphor basic material and asubstrate 7 to 60 cm; controlling a temperature of the substrate; andevaporating the photostimulable phosphor basic material at 1.0 ×10⁻² Pawith an evaporation speed of 0.5 μm/min or more, to form aphotostimulable phosphor in the photostimulable phosphor layer by avapor phase manner.

[0022] According to the first aspect of the invention, it is possible toprovide a radiographic image conversion panel which is excellent inluminance, sharpness and X-ray absorption rate.

[0023] In accordance with a second aspect of the invention, theradiographic image conversion panel is produced by the method of thefirst aspect, wherein the photostimulable phosphor layer of theradiographic image conversion panel has a thickness of 50 to 120 μm andan X-ray absorption amount of 70 to 95%.

BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The present invention will become more fully understood from thedetailed description given hereinbelow and the accompanying drawingswhich are given by way of illustration only, and thus are not intendedas a definition of the limits of the present invention, and wherein;

[0025]FIG. 1 is a schematic view showing a construction example using aradiographic pattern conversion panel according to an embodiment of thepresent invention.

PREFERRED EMBODIMENTS OF THE INVENTION

[0026] Embodiments of the invention will be described in detail.

[0027] 1. A first aspect of the invention is a method for manufacturinga radiographic image conversion panel having a photostimulable phosphorlayer on a support, comprising: setting a distance between aphotostimulable phosphor basic material and a substrate 7 to 60 cm;controlling a temperature of the substrate; and evaporating thephotostimulable phosphor basic material at 1.0×10⁻² Pa with anevaporation speed of 0.5 μm/min or more, to form a photostimulablephosphor in the photostimulable phosphor layer by a vapor phase method.

[0028] 2. In the method of paragraph 1, preferably, the evaporationspeed is 0.5 to 10 μm/min.

[0029] 3. Preferably, the controlling a temperature of the substrate isperformed by cooling.

[0030] 4. In the method of paragraph 3, preferably, the coolingcomprises controlling the temperature of the substrate in a range of 10to 200° C.

[0031] 5. A second aspect of the invention is a radiographic imageconversion panel produced by the method of paragraph 1, wherein thephotostimulable phosphor layer of the radiographic image conversionpanel has a thickness of 50 to 120 μm and an X-ray absorption amount of70 to 95%.

[0032] 6. In the panel of paragraph 5, preferably, the photostimulablephosphor layer contains a photostimulable phosphor which makes alkalihalide represented by a general formula (1) a host,

M¹X·aM²X′·bM³X″:eA   (1)

[0033] where M¹ represents at least one alkali metal atom selected fromatoms of Li, Na, K, Rb and Cs; M² represents at least one bivalent metalatom selected from atoms of Be, Mg, Ca, Sr, Ba, Zn, Cd, Cu and Ni; M³represents at least one trivalent metal atom selected from atoms of Sc,Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Gaand In; X, X′ and X″ represent at least one halogen atom selected fromatoms of F, Cl, Br and I; A is at least one metal atom selected fromrespective atoms of Eu, Tb, In, Ce, Tm, Dy, Pr, Ho, Nd, Yb, Er, Gd, Lu,Sm, Y, Tl, Na, Ag, Cu and Mg; and a, b and e satisfy 0<a≦0.5, 0≦b<0.5and 0<e≦0.2.

[0034] 7. In the radiographic image conversion panel of paragraph 5,preferably, an average particle diameter of phosphor particles at anextremity of phosphor crystals in the photostimulable phosphor layer isin a range of 0.1 to 5 μm.

[0035] Preferred embodiments of the invention will be described infurther detail.

[0036] In the method for manufacturing a radiographic image conversionpanel having a photostimulable phosphor layer (hereinafter may be simplyreferred to as phosphor layer) on a support, according to the firstaspect of the present invention, at least one photostimulable phosphorlayer is formed of a photostimulable phosphor by evaporating phosphorbasic materials at an evaporation speed of 0.5 μm/min or more,preferably, 0.5 to 10 μm/min. In the method, it is preferable that astep of controlling a substrate temperature is a cooling one to enhancethe advantageous effects of the invention.

[0037] That is, it is possible to obtain a phosphor layer having finecolumnar crystals, enhance a filling factor of a phosphor in thephosphor layer and consequently obtain a radiographic image conversionpanel excellent in sharpness by making a distance betweenphotostimulable phosphor basic materials and a substrate 7 to 60 cm,controlling the substrate temperature and making the evaporation speedof the phosphor basic materials 0.5 to 10 μm/min.

[0038] Also, as a result of various studies, the present inventors havefound that variation of crystal diameters in crystal growth can becontrolled by cooling the substrate because the substrate temperature israised as temperature is raised by heating due to evaporation on thesubstrate, the crystal diameters gradually thicken and the crystalsbecome corn-shape to extremely reduce the sharpness.

[0039] The substrate cooling was performed by water cooling and anelectrostatic chuck was used for adhesion of a substrate coolingsection. It is preferred that a cooling temperature is from 10 to 200°C. by cooling the substrate.

[0040] In the invention, it is preferable that a film thickness of atleast one photostimulable phosphor layer becomes less than 120 μm and anX-ray absorption amount of the photostimulable phosphor layer (X-rayabsorption rate) is from 70 to 95% by manufacturing the radiographicimage conversion panel by the above method for manufacturing theradiographic image conversion panel.

[0041] As a result of further study, the present inventors have foundthat to increase the X-ray absorption amount on a thin film, an averageparticle diameter of the crystal extremities can be reduced byincreasing column developing points at an initial stage of columnarcrystals developed on the substrate and making the average particlediameter at the crystal extremities of the phosphor 0.1 to 5 μm, andthat it becomes possible to maintain the excellent sharpness by a lightguiding (fiber) effect.

[0042] The higher concentrations of evaporation and vapor are, the moredeveloping points are developed at the initial stage of the columnarcrystals.

[0043] The evaporation or vapor concentration is identical to anevaporation speed. The faster the evaporation speed is, the higher theevaporation or vapor concentration is. Thus it is possible to suppresscrystal growth and increase the developing points at the initial stageof columnar crystals.

[0044] Whether the developing points at the initial stage of columnarcrystals are many or few can be confirmed by measuring a width of columnaround the substrate against an extremity diameter of the columnarcrystal by an SEM photograph of a crystal section.

[0045] Therefore, in the invention, the evaporation speed of anevaporation source is from 0.5 to 10 μm/min or more, consequently thefilm thickness of the photostimulable phosphor layer becomes from 50 to120 μm and the X-ray absorption amount of the photostimulable phosphorlayer becomes from 70 to 95%. Thus it is possible to obtain theradiographic image conversion panel with high luminance and highsharpness which is excellent in X-ray absorption rate.

[0046] In the invention, it is preferable to manufacture thephotostimulable phosphor layer of the invention by an applicationmanner. The photostimulable phosphor layer is composed mainly of thephosphor and high molecular resin, and coated and formed on the supportusing a coater.

[0047] As the photostimulable phosphor which can be used for the coatingtype phosphor layer, generally used are photostimulable phosphors whichexhibit photostimulated luminescence at a wavelength range of 300 to 500nm by excitation light at a wavelength range of 400 to 900 nm.

[0048] The photostimulable phosphor represented by the above generalformula (1) preferably used for the invention will be illustrated below.

M¹X·aM²X′·bM³X″:eA   General formula (1)

[0049] As for the photostimulable phosphor represented by theformer-described formula (1), M¹ represents at least one kind of alkalimetal selected from Li, Na, K, Rb, Cs and the like. Among them, at leastone kind of alkali metal selected from Rb and Cs is preferable, and Csis more preferable.

[0050] M² represents at least one kind of bivalent metal selected fromBe, Mg, Ca, Sr, Ba, Zn Cd, Cu, Ni and the like. Among them, a bivalentmetal selected from Be, Mg, Ca, Sr and Ba is preferable.

[0051] M³ represents at least one kind of trivalent metal selected fromSc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al,Ga, In and the like. Among them, a trivalent metal selected from Y, Ce,Sm, Eu, Al, La, Gd, Lu, Ga and In is preferable.

[0052] A represents at least one kind of metal selected from Eu, Tb, In,Ce, Tm, Dy, Pr, Ho, Nd, Yb, Er, Gd, Lu, Sm, Y, Tl, Na, Ag, Cu and Mg,and is preferably Eu metal atom.

[0053] From the viewpoint of improving photostimulated luminescenceluminance of a photostimulable phosphor, X, X′ and X″ represent at leastone kind of halogen selected from F, Cl, Br and I, among them,preferably at least one kind of halogen selected from Br and I. At leastone kind of halogen selected from Br and I is more preferable.

[0054] In the chemical compound represented in the general formula (1),a is 0≦a<0.5, preferably 0≦a<0.01, and b is 0≦b<0.5, preferably0≦b≦10⁻², and e is 0<e≦0.2, preferably 0<e≦0.1.

[0055] Used as for the materials of the phosphor are;

[0056] (a) at least one kind of chemical compound selected from NaF,NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbF, RbCl, RbBr, RbI, CsF, CsCl, CsBrand CsI,

[0057] (b) at least one kind of chemical compound selected from MgF₂,MgCl₂, MgBr₂, MgI₂, CaF₂, CaCl₂, CaBr₂, CaI₂, SrF₂, SrCl₂, SrBr₂, SrI₂,BaF₂, BaCl₂, BaBr₂, BaBr₂.2H₂O, BaI₂, ZnF₂, ZnCl₂, ZnBr₂, ZnI₂, CdF₂,CdCl₂, CdBr₂, CdI₂, CuF₂, CuCl₂, CuBr₂, CuI, NiF₂, NiCl₂, NiBr₂ andNiI₂, and

[0058] (c) a halide compound having at least one kind of trivalent metalselected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,Yb, Lu, Al, Ga and In.

[0059] (d) As for materials of the activator, a compound having a metalselected from Eu, Tb, In, Cs, Ce, Tm, Dy, Pr, Ho, Nd, Yb, Er, Gd, Lu,Sm, Y, Tl, Na, Ag, Cu and Mg.

[0060] The phosphor materials of above-described (a) to (d) are weighedso that the factors a, b and e in the mixed composition according to thegeneral formula (1) are within the above-described ranges, and dissolvedin pure water.

[0061] Where the materials can be mixed with mortar, ball mill, mixermill and the like. After the pH value C is regulated to 0<C<7 with apredefined acid, water content of the solution is evaporated.

[0062] Among the above photostimulable phosphors, it is preferred thatthe photostimulable phosphor particles contain iodine. For example,iodine-containing bivalent europium-activated alkali earth metalfluoride halide type phosphors, iodine-containing bivalenteuropium-activated alkali earth metal halide type phosphors,iodine-containing rare earth element-activated rare earth oxy halidetype phosphors, and iodine-containing bismuth-activated alkali metalhalide type phosphors are preferable because they exhibitphotostimulated luminescence with high luminance, and particularly it ispreferred that the photostimulable phosphor is an Eu addition BaFIcompound.

[0063] In the invention, as examples of binders used for the phosphorlayer, it is possible to include binders of which representatives areproteins such as gelatin, polysaccharides such as dextran, or naturalhigh molecular substances such as gum arabic, and synthetic highmolecular substances such as polyvinyl butyral, polyvinyl acetate,nitrocellulose, ethylcellulose, vinylidene chloride, vinyl chloridecopolymer, polyalkyl(meth)acrylate, vinyl chloride, vinyl acetatecopolymer, polyurethane, cellulose acetate butyrate, polyvinyl alcoholand linear polyester, and the like. But, the invention is characterizedin that the binder is a resin making thermoplastic elastomer a majoringredient. As the thermoplastic elastomer, for example, included arepolystyrene-type thermoplastic elastomers described above, polyolefintype thermoplastic elastomers, polyurethane type thermoplasticelastomers, polyester type thermoplastic elastomers, polyamide typethermoplastic elastomers, polybutadiene type thermoplastic elastomers,ethylene vinyl acetate type thermoplastic elastomers, polyvinyl chloridetype thermoplastic elastomers, natural gum type thermoplasticelastomers, fluorine gum type thermoplastic elastomers, polyisoprenetype thermoplastic elastomers, chlorinated polyethylene typethermoplastic elastomers, styrene-butadiene gum and silicon gum typethermoplastic elastomers, and the like.

[0064] In these, the polyurethane type thermoplastic elastomers and thepolyester type thermoplastic elastomers are preferable becausedispersibility is good since a binding force with the phosphor isstrong, ductility is rich and flexibility against radiation sensitizingscreen becomes good. These binders may be those which are crosslinkedwith a crosslinker.

[0065] A mixing ratio of the binder to the photostimulable phosphor in acoating solution varies depending on a determined value of Hayes rate ofthe aimed radiographic image conversion panel, but is preferably from 1to 20 parts by mass and more preferably from 2 to 10 parts by pass basedon the phosphor.

[0066] As organic solvents used for the preparation of thephotostimulable phosphor layer coating solution, for example, includedare lower alcohol such as methanol, ethanol, isopropanol and n-butanol,ketone such as acetone, methylethylketone, methylisobutylketone andcyclohexane, ester of lower fatty acid and lower alcohol such as methylacetate, ethyl acetate and n-butyl acetate, ether such as dioxane,ethyleneglycol monoethylether and ethyleneglycol monomethylether,aromatic compounds such as triol and xylol, hydrocarbon halide such asmethylene chloride and ethylene chloride, and the mixtures thereof.

[0067] In the coating solution, various additives may be mixed such as adispersant to enhance the dispersibility of the phosphor in the coatingsolution and a plasticizer to enhance a binding force between the binderand the phosphor in the photostimulable phosphor layer after theformation. Examples of the dispersants used for such a purpose, it ispossible to include phthalic acid, stearic acid, caproic acid,lipophilic surfactants and the like. Examples of the plasticizers, it ispossible to include phosphate ester such as triphenyl phosphate,tricresyl phosphate and diphenyl phosphate, phthalate ester such asdiethyl phthalate and dimethoxyethyl phthalate, glycolate ester such asethylphthalylethyl glycolate and butylphthalylbutyl glycolate; andpolyester of polyethyleneglycol and aliphatic dibasic acid such aspolyester of triethyleneglycol and adipic acid and polyester ofdiethyleneglycol and succinic acid. Also, the dispersant such as stearicacid, phthalic acid, caproic acid and lipophilic surfactant may be mixedin the photostimulable phosphor layer coating solution for the purposeof enhancing the dispersibility of photostimulable phosphor particles.

[0068] The preparation of the photostimulable phosphor layer coatingsolution is carried out using a dispersing apparatus such as a ballmill, bead mill, sand mill, attritor, three roll mill, high speedimpeller dispersing machine, Kady mill, or ultrasonic dispersingmachine, and the like.

[0069] A coating film is formed by evenly coating the coating solutionprepared as the above on the support surface described below. As coatingmethods which can be used, it is possible to use common coating meanssuch as a doctor blade, roll coater, knife coater, comma coater, lipcoater, and the like.

[0070] The coating film formed by the above means is subsequently heatedand dried to complete the formation of the photostimulable phosphorlayer on the support. A film thickness of the photostimulable phosphorlayer varies depending on properties of the aimed radiographic imageconversion panel, types of the photostimulable phosphor, the mixingratio of the binder to the phosphor and the like, but is from 0.5 μm to1 mm, preferably from 10 to 500 μm, more preferably from 50 to 120 μm,in the invention.

[0071] A substance with high absorption of light and a substance withhigh reflection of light may be contained in the photostimulablephosphor layer, and this is effective for reduction of light diffusionof photostimulated excitation light which enters in the photostimulablephosphor layer toward a horizontal direction.

[0072] Here, substances having high light reflectance designatesubstances having high light reflectance for photostimulated excitationlight (500 to 900 nm, especially 600 to 800 nm). Aluminum, magnesium,silver, indium, other metals, white pigments and coloring materials ofgreen to red can be given as examples. White pigments can also reflectphotostimulated luminescence.

[0073] As for the white pigments, TiO₂ (anatase and rutile type), MgO,PbCO₃, Pb(OH)₂, BaSO₄, Al₂O₃, M_((II))FX (M_((II)) is at least one kindof element selected from Ba, Sr and Ca, and X is either Cl or Br.),CaCO₃, ZnO, Sb₂O₃, SiO₂, ZrO₂, lithopone (BaSO₄.ZnS), magnesiumsilicate, anionic silico-sulfate, anionic lead phosphate and aluminumsilicate are given as examples.

[0074] These white pigments disperse photostimulated luminescence easilyby reflection or refraction of light since they have high hiding powerand refractive index. As a result, these substances can improve thesensitivity of the radiographic image conversion panel markedly.

[0075] As for the substances of high absorptivity, such like carbonblack, chromium oxide, nickel oxide and iron oxide, and blue colormaterials are given as examples. Among them, carbon black also absorbsphotostimulated luminescence.

[0076] Further, both organic and inorganic system color materials areavailable as the color materials described above. As the organic systemcolor materials, Zabon Fast Blue 3G (produced by Hoechst), Estrol BrillBlue N-3RL (produced by Sumitomo Chemical), D & C Blue No. 1 (producedby National Aniline), Spirit Blue (produced by Hodogaya Chemical), OilBlue No. 603 (produced by Orient), Kiton Blue A (produced byChiba-Geigy), Aizen Catiron Blue GLH (produced by Hodogaya Chemical),Lake Blue AFH (produced by Kyowa Sangyo), Primocyanine 6GX (produced byInabata & Co.), Brill Acid Green 6BH (produced by Hodogaya Chemical),Cyan Blue BNRCS (produced by Toyo Ink), Lionoil Blue (produced by ToyoInk) and the like can be used.

[0077] Further, organic system metal complex salt color materials suchas color index Nos. 24411, 23160, 74180, 74200, 22800, 23154, 23155,24401, 14830, 15050, 15760, 15707, 17941, 74220, 13425, 13361, 13420,11836, 74140, 74380, 74350, 74460 and the like can be given.

[0078] As for the inorganic system color materials, for example,inorganic pigment such as permanent blue, cobalt blue, cerulean blue,chromium oxide, TiO₂—ZnO—Co—NiO system and the like can be given.

[0079] Further, a photostimulable phosphor layer of the presentinvention can comprise a protective layer.

[0080] A protective layer can be manufactured by applying an embrocationof the protective layer directly to the photostimulable phosphor layer,adhering a separately formed protective layer is adhered to thephotostimulable phosphor layer, or forming a photostimulable phosphorlayer is directly formed on a previously formed protective layer.

[0081] As for materials of the protective layer, general materials for aprotective layer is used such as cellulose acetate, nitrocellulose,polymethyl methacrylate, polyvinyl butyral, polyvinyl folmal,polycarbonate, polyester, polyethylene terephthalate, polyethylene,polyvynilidene chloride, nylon, polytetrafluoroethylene,polytriflurochloroethylene, tetrafluoroethylene-hexafluoropropylenecopolymer, vinylidene chloride-vinyl chloride copolymer, vinylidenechloride-acrylonytrile copolymer and the like. A transparent glass sheetis also available as a protective layer.

[0082] The layer thickness of these protective layers is preferably 0.1to 2000μm.

[0083]FIG. 1 is a schematic view showing an example of a structure ofradiographic image conversion panel according to the present invention.

[0084] In FIG. 1, a reference numeral 21 designates a radial raygenerator, 22 designates a subject, 23 designates a radiographic imageconversion panel comprising a visible or infrared light photostimulablephosphor layer having a photostimulable phosphor, 24 designates aphotostimulated excitation light source to emit a radial ray latentimage of radiographic image conversion panel 23 as photostimulatedluminescence, 25 designates a photoelectric converter to detect thephotostimulated luminance emitted from a radiographic image conversionpanel 23, 26 designates a image playback equipment to replayphotoelectric signals detected by a photoelectric converter 25 as animage, 27 designates a image display unit which display the reproducedimage, 28 designates a filter that cut the reflected light and transmitthe light only emitted from a radiographic image conversion panel 23.

[0085] In addition, FIG. 1 shows an example of obtaining a radial raytransmitted image of a subject. When a subject 22 itself radiates radialray, the above-described radial ray generator 21 is not particularlyrequired.

[0086] The photoelectric converter 25 or later have only to replayinformation of light as an image of some kind, and are not limited tothe above-described system.

[0087] As shown in FIG. 1, the subject 22 is set between a radial raygenerator 21 and a radiographic image conversion panel 23, and radialray R is radiated. Then radial ray R transmits a subject 22 according toa variety of transmittance of the each part in the subject 22. Thetransmission image RI (that is, an image of strong and weak of radialray) incidents to a radiographic image conversion panel 23.

[0088] A photostimulable phosphor layer of the radiographic imageconversion panel 23 absorbs the incidented transmission image RI. Thenelectrons and/or pores, the number of which is proportional to theamount of radiation absorbed in photostimulable phosphor layer, aregenerated to accumulate the trap level of a photostimulable phosphor.

[0089] That is, a latent image in which the energy of a transmittedradial ray image is accumulated is formed. Succusesively the latentimage is elicited by excitation of light energy.

[0090] A photostimulated excitation light source 24 irradiates visibleor infrared light to a photostimulable phosphor layer. The electronsand/or pores accumulated in the trap level are flushed and accumulatedenergy is emitted as photostimulated luminescence.

[0091] The strength of the emitted photostimulated luminescence isproportional to the number of the accumulated electron and/or pores,e.g. the amount of radial ray energy absorbed in a photostimulablephosphor layer of the radiographic image conversion panel 23. This lightsignal is converted to an electric signal with a photoelectric converter25, for example, such as a photoelectric multiplier, subsequentlyreplayed with an image playback equiμment 26, and displayed with animage display 27.

[0092] The image playback equipment 26 is more effective if it does notsimply replay an electric signal as an image signal, but also canperform so called image processing and calculation, memory and storageof an image.

[0093] The emitted photostimulable luminescence desirably has thespectrum distribution in as shorter wavelength band as possible. Becausea light is required to be separated into reflection light ofphotostimulated excitation light and photostimulated luminescenceemitted from a photostimulable phosphor layer when it is exited by lightenergy, and a photoelectric converter which detects the luminescenceemitted from photostimulable phosphor layer generally has highersensitivity for light energy of wavelength 600 nm or less.

[0094] The photostimulable phosphor of the present invention fills theabove-described parameters simultaneously, since the luminescencewavelength band of the photostimulable phosphor of the present inventionis between 300 and 500 nm while the photostimulated excitationwavelength band is between 500 and 900 nm. In resent years, sincediagnostic unit has been downsized, a laser diode, which has high poweroutput and is to be compacted easily, is preferably used, and thepreferable wavelength of the laser diode is 680 nm. The photostimulablephosphor applied to the radiographic image conversion panel of thepresent invention shows remarkably fine sharpness when excitationwavelength is 680 nm.

[0095] In other words, every photostimulable phosphor of the presentinvention shows a luminescence having the main peak thereof at 500 nm orless. Since the luminescence is easily separated from excitation lightand the wavelength of the luminescence accords with spectral sensitivityof a photodetector, the photostimulated luminescence is effectivelydetected. As a result, the sensitivity of image receiving system isimproved because of high efficiency of light detection.

[0096] A spectrum of a light source used in photostimulated excitationlight source 24 includes photostimulated excitation wavelength thephotostimulable phosphor used in a radiographic image conversion panel23. Particularly, when a laser diode is used, the optical system becomessimple and the excitation light luminance becomes high. Since efficiencyof photostimulated luminescence is improved, more preferable results canbe obtained.

[0097] For example, as for the laser, He—Ne laser, He—Cd laser, Ar ionlaser, Kr ion laser, N₂ laser, YAG laser and its second harmonic, rubylaser, semiconductor laser, all kinds of dye laser, metal vapor lasersuch as cupper vapor laser and the like can be applied. Normallycontinuous oscillation laser such like He—Ne laser and Ar ion laser isdesirable. Pulse oscillation laser is also available when and the pulseof laser is synchronized with scanning cycle of each pixel in a panel.

[0098] If a delay of a luminescence is utilized to separate a light, asdisclosed in JP-Tokukaisho-59-22046A, pulse oscillation laser is morepreferable than modulated continuous oscillation laser.

[0099] In the above-described laser light sources, semiconductor laseris particularly preferably available because of its small size,affordable price and furthermore needlessness of a modulator.

[0100] A filter 28 is selected according to a combination ofphotostimulated luminescence wavelength of a photostimulable phosphorincluded in a radiographic image conversion panel 23 and photostimulatedexcitation light wavelength of photostimulated excitation light source24, since the filter transmits the photostimulated luminescence emittedfrom a radio graphic image conversion panel 23 and interceptphotostimulated excitation light.

[0101] For example, in practically preferable combination such thatexcitation wavelength is 500 to 900 nm and photostimulated luminancewavelength is 300 to 500 nm, glass filters from blue to violet such asC-39, C-40, V-40, V-42 and V-44 (Toshiba Co. ltd.), 7-54 and 7-59(Corning Co. Ltd.), BG-1, BG-3, BG-25, BG-37 and BG-38 (Spectrofilm Co.Ltd.) and the like are available as the filter. An interference filterhaving any property on some level also can be used. As for thephotoelectrical converter 25, any devices that convert variation oflight intensity to that of electric signal are available such asphotoelectric tube, photoelectric multiplier, photodiode,phototransistor, solar battery, photoconductive cell and the like.

EXAMPLE

[0102] The present invention is specifically illustrated by referring toexamples, but embodiments of the invention is not limited thereto.

Example 1

[0103] <Manufacture of Radiographic Image Conversion Panel Samples 1 to8 (Samples 1 to 8)>

[0104] (Manufacture of Photostimulable Phosphor)

[0105] <Phosphor Particles—Coating>

[0106] A photostimulable phosphor was obtained by filling CsBr:Eu basicmaterials prepared to become CsCO₃ such that an Eu amount is 5/10,000mol based on 1 mol of CsBr in a molybdenum boat and evaporating at avacuum state of 1.0×10⁻² Pa and at an evaporation speed of 10 μm/minwith a distance to a substrate of 28 cm (an average particle diameter ofphosphor particles at the extremity of phosphor crystal was 4.9 μm). Asubstrate temperature is controlled at 150° C.

[0107] With respect to an average particle diameter of phosphorparticles at the extremity of the phosphor crystal, particle diametersof 100 phosphor particles at the extremity of the phosphor crystal wereobtained by an electron microscope, and an average value thereof wasrendered the average particle diameter.

[0108] In order to form the phosphor layer, the above phosphor and apolyester solution (Vylon 63ss supplied from Toyobo Co., Ltd.) weremixed/dispersed as a resin solution of 5% by mass of the phosphor with asolid concentration of 95% by mass to make a coating material.

[0109] The photostimulable phosphor layer was formed by coating thiscoating material on a support of 188 μm polyethylene terephthalate film(188×30 supplied from Toray Industries, Inc.) and coating/drying inthree drying zones of 80° C., 100° C. and 110° C. in an inert oven undera drying atmosphere of Ar at a CS (coating speed) of 2 m/min.

[0110] The support having the above photostimulable phosphor layer wasplaced in a barrier bag (GL-AE relief printing) to which backside ALfoil was attached, and sealed to make the radiographic patternconversion panel sample 1 (sample 1).

[0111] The radiographic pattern conversion panel samples 2 to 5 (samples2 to 5) were made as is the case with the sample 1, except forcontrolling the evaporation speed, the distance between the phosphorbasic materials and the substrate, and the substrate temperature asdescribed in Table 1.

[0112] For respective samples, the following evaluations were carriedout.

[0113] <Evaluation of Sharpness>

[0114] The sharpness of the radiographic image conversion panel samplewas evaluated by obtaining a modification transmission function (MTF).

[0115] MTF was obtained by attaching a CTF chart on the radiographicimage conversion panel sample, subsequently irradiating 80 kVp of X-rayat 10 mR (distance to a subject: 1.5 m) on the radiographic imageconversion panel sample, and then scanning/reading a CTF chart patternusing semiconductor laser with a diameter of 100 μmφ (680 nm: power onthe panel, 40 mW). A value in the table is represented by a value where2.01 p/mm of MTF value was added.

[0116] <Evaluation of Luminance and Luminance Distribution (UnevenLuminance)>

[0117] The luminance was evaluated using Regius 350 supplied from KonicaCorporation.

[0118] As with the evaluation of sharpness, after irradiating X-ray by atungsten bulb at 80 kVp and 10 mAs with a distance of 2 m between anexpose radiation source and a plate, luminance was read by placing theplate in Regius 350. The evaluation was performed on the basis ofelectric signals obtained from the photomultiplier.

[0119] Electric signal distribution from the photomultiplier in apicturized face was relatively evaluated, and a standard deviation wascalculated to make a luminance distribution (S.D.) of each sample. Thesmaller a value is, the less the uneven luminance is.

[0120] <Measurement of X-Ray Absorption Amount>

[0121] An arrival X-ray amount: B was measured using an ionization typedosimeter (Ionex Dose Master 2590 B supplied from Toyo Medic Co., Ltd.)disposed at a location at 105 cm from a molybdenum anode of the targettube, by transmitting X-ray generated from a molybdenum target tubedriven at 28 kVp through a molybdenum filter with a thickness of 0.03mm, and performing X-ray irradiation under a condition at 64 mA·sec.

[0122] Then, an X-ray amount: D which transmitted through theradiographic pattern conversion panel was measured using the ionizationtype dosimeter by disposing the radiographic pattern conversion panel ata location at 100 cm from the molybdenum anode of the target tube andperforming the X-ray irradiation under the same condition as the above,and an X-ray absorption amount was calculated by the followingcalculation formula.

X-ray absorption amount (%)=(D/B)×100

[0123] In the table, the samples 1 to 3 and 5 are the samples of thepresent invention, and the sample 4 is the sample for comparison.

[0124] As obvious from Table 1, it is understood that the samples of theinvention are more excellent than the sample for comparison. TABLE 1Absorption Particle Evaporation Distance to Substrate Uneven Amount ofDiameter at Speed Substrate Temperature MTF Luminance X-ray at 28 kVExtremity μm/min cm Control ° C. Luminance (21 p/mm) (S.D.) (%) (μm)Sample 1 10 28 Yes 150 1.67 32% 10 70 4.9 Sample 2 20 28 Yes 150 1.8233% 8 85 3.8 Sample 3 40 28 Yes 150 2.54 41% 7 95 2.7 Sample 4 5 28 No260 0.43 7% 46 65 12.2 Sample 5 40 65 Yes 150 1.22 32% 9 89 4.2

[0125] As shown in the example, the radiographic image conversion paneland the method for manufacturing the radiographic image conversion panelaccording to the invention are inexpensive, excellent in luminance, evenluminance and sharpness, and have an excellent effect in X-rayabsorption amount (absorption rate).

[0126] The entire disclosure of Japanese Patent Application No.2003-079230 which was filed on Mar. 24, 2003, including specification,claims, drawings and abstract, is incorporated into the presentinvention in its entirety.

What is claimed is:
 1. A method for manufacturing a radiographic imageconversion panel having a photostimulable phosphor layer on a support,comprising: setting a distance between a photostimulable phosphor basicmaterial and a substrate 7 to 60 cm; controlling a temperature of thesubstrate; and evaporating the photostimulable phosphor basic materialin a vacuum of 1.0×10⁻² Pa with an evaporation speed of 0.5 μm/min ormore, to form a photostimulable phosphor in the photostimulable phosphorlayer by a vapor phase method.
 2. The method of claim 1, wherein theevaporation speed is in a range of 0.5 to 10 μm/min.
 3. The method ofclaim 1, wherein the controlling a temperature of the substrate isperformed by cooling.
 4. The method of claim 3, wherein the coolingcomprises controlling the temperature of the substrate in a range of 10to 200° C.
 5. A radiographic image conversion panel manufactured by themethod of claim 1, wherein the photostimulable phosphor layer of theradiographic image conversion panel has a thickness of 50 to 120 μm andan X-ray absorption amount of 70 to 95%.
 6. The panel of claim 5,wherein the photostimulable phosphor layer contains a photostimulablephosphor which makes alkali halide represented by a general formula (1)a host, M¹X·aM²X′·bM³X″:eA   (1) where M¹ represents at least one alkalimetal atom selected from atoms of Li, Na, K, Rb and Cs; M² represents atleast one bivalent metal atom selected from atoms of Be, Mg, Ca, Sr, Ba,Zn, Cd, Cu and Ni; M³ represents at least one trivalent metal atomselected from atoms of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Lu, Al, Ga and In; X, X′ and X″ represent at least onehalogen atom selected from atoms of F, Cl, Br and I; A is at least onemetal atom selected from respective atoms of Eu, Tb, In, Ce, Tm, Dy, Pr,Ho, Nd, Yb, Er, Gd, Lu, Sm, Y, Tl, Na, Ag, Cu and Mg; and a, b and esatisfy 0≦a<0.5, 0≦b<0.5 and 0<e≦0.2.
 7. The radiographic imageconversion panel of claim 5, wherein an average particle diameter ofphosphor particles at an extremity of phosphor crystals in thephotostimulable phosphor layer is in a range of 0.1 to 5 μm.